Polymerization of olefinic-containing monomers employing anionic initiators

ABSTRACT

Process for anionically polymerising a conjugated 1,3-diene monomer consists of contacting the monomer in an inert hydrocarbon solvent with a monofunctional silyl ether initiator of general formula R 1  R 2  R 3  Si--O--A--Li where R 1  to R 3  are independently selected from monovalent organic substituent groups and A is a short chain hydrocarbon bridging group, to yield a polydiene having a molecular weight of typically 1,000-10,000, a high 1.4 content of typically 90% and a low polydispensity of typically 1.15. The reactive ends of the living polymer chains may be terminated with a reactive group such as hydroxyl by treating the polymer with ethylene oxide. Subsequent removal of the polymer&#39;s relatively unreactive silyl end groups by reaction with tetra-n-butylammonium fluoride produces a difunctional, chain-extendable, hydroxy-terminated polydiene useful as a rubbery binder prepolymer.

This invention relates to a process for the polymerisation ofolefinic-containing monomers employing anionic initiators. The inventionalso relates to novel anionic initiators for use in said process, and topolymers produced by said process.

Highly useful polymeric products can be obtained by polymerisingolefinic-containing monomers in the presence of an organo-alkali metalinitiator and subsequently reacting the resulting polymer, containing anactive alkali metal end group or groups, with a reagent which willeither couple the polymer molecules or replace the alkali metal withmore stable reactive end groups.

It can be seen that such a polymerisation process will consistessentially of three stages:

a. Initiation, in which the monomeric material is contacted with amonofunctional or difunctional anionic initiator.

b. Propagation, in which the monomer is allowed to polymerise to formliving polymer chains with negatively charged ends, and

c. Terminator, in which the living polymer chains are treated withsuitable reagents, generally to form monofunctionally or difunctionallyterminated polymers.

The presence of a reactive terminal group or groups on the ends of thepolymer molecules enables substantially more effective cures to takeplace. In the case of a polymer containing a reactive group on each ofits ends (a telechelic polymer) all of the polymer molecule will be tiedinto the cross-linked structure of the cured material.

The well defined structure produced by telechelic polymers in thenetworks of their cured products is the primary reason for theirincreased use as precursors in the commercial production of curedrubbery solids.

However, in order to meet the requirements of a modern synthetic rubberit is not enough that the polydiene produces effective cures nor thatthe cured product has a well defined cross linked structure, it is alsoimportant that the cured product possesses good elastomeric properties.In the case of polydienes the elastomeric quality of the cured productis dependent upon the 1,4-content of the polymeric diene. Generally, thehigher the 1,4-content of the polymer, the lower its glass transitiontemperature and the better the elastomeric properties of the curedproduct. It follows from this that any process chosen for the commercialproduction of polydienes (in particular telechelic polymers of1,3-dienes) must lead to a material having a high 1,4-content.

It is well known that monofunctional polyalkenes and high 1,4-contentmonofunctional polydienes can be prepared in inert non-polar hydrocarbonsolvents by initiating the reaction with a monofunctional anionicinitiator such as butyl lithium. The preparations of telechelicpolydienes, using corresponding difunctional initiators such as1,4-dilithiobutane, has hitherto required that the anionicpolymerisation reaction (propagation) takes place in the presence of asterically-hindered Lewis acid in order to ensure that the polymericproduct possesses a reasonable 1,4-content (typically 25-50%).Furthermore, the polymerisation reaction must take place in polarsolvents such as alkyl and cycloalkyl ethers because difunctionalinitiators are insoluble in non-polar solvents such as hydrocarbons, andthis has hitherto prevented the formation of polydienes with1,4-contents above about 50% which can be produced using theaforementioned monofunctional initiators in hydrocarbon solvents.

A further disadvantage associated with the use of difunctionalinitiators is that the choice of telechelic polymers which can beproduced at the termination of propagation is restricted to those havingidentical terminal groups at either end since the reagent used fortermination will react in a similar manner with both living ends of thegrowing polymer chain.

The main object of the present invention is to provide a new process forthe anionic polymerisation of an olefinic-containing monomer which canbe used to prepare telechelic polymers and yet avoids the disadvantagesassociated with the use of known difunctional initiators. It is afurther object of the present invention to provide a process for theanionic polymerisation of a conjugated 1,3-diene which produces apolymeric material having an enhanced 1,4-content. It is a yet furtherobject of the invention to provide a novel anionic initiator for use inthe present process.

According to the present invention, there is provided a process for theanionic polymerisation of an olefinic-containing monomer comprisingcontacting the monomer in an inert solvent with a monofunctional silylether initiator of general formula I ##STR1## wherein R¹, R² and R³ areindependently selected from saturated and unsaturated aliphatic andaromatic radicals, A is a hydrocarbon bridging group containing from 1to 25 carbon atoms and B is an alkali metal.

The inert solvent is preferably a non-polar solvent such as ahydrocarbon, since anionic polymerisation in the presence of suchsolvents is known to produce, from 1,3-dienes, polydienes with high1,4-contents. Preferred solvents are aliphatic, alicyclic and aromatichydrocarbons, especially alkanes, cycloalkanes and cycloalkenes, havingfrom 3 to 12, preferably from 4 to 8, carbon atoms. Examples of suitablehydrocarbons are hexane, cyclohexane, toluene and benzene. Alkanes arethe most preferred solvents.

The olefinic monomer is preferably an alkene or a 1,3-diene. The alkeneor 1,3-diene will be chosen from the group of unsaturated organiccompounds that can be polymerised anionically (i.e. in a reactioninitiated by an organo alkali metal). Suitable alkenes include theoptionally-substituted styrenes and vinylnaphthalenes. Suitable1,3-dienes will preferably contain from 4 to 12, especially from 4 to 8,carbon atoms per molecule. Examples of these compounds include thefollowing: 1,3-butadiene; isoprene; 2,3-dimethyl-1,3-butadiene;1,3-pentadiene; 2-methyl-3-ethyl-1,3-butadiene; 3-methyl-1,3-butadiene;2-methyl-3-ethyl-1,3-pentadiene; 1,3-hexadiene; 2-methyl-1,3-hexadiene;1,3-heptadiene; 3-methyl-1,3-heptadiene; 1,3-octadiene;3-butyl-1,3-octadiene; 3,4-dimethyl-1,3-hexadiene;3-n-propyl-1,3-pentadiene; 4,5-diethyl-1,3-octadiene;phenyl-1,3-butadiene; 2,4-diethyl-1,3-butadiene;2,3-di-n-propyl-1,3-butadiene; and 2-methyl-3-isopropyl-1,3-butadiene.

Among the dialkylbutadienes, it is preferred that the alkyl groupscontain from 1 to 3 carbon atoms. Of the above monomers 1,3-butadiene,isoprene, 2,3-dimethyl-1,3-butadiene and 1,3-pentadiene are preferredwith 1,3-butadiene being particularly preferred. The dienes may bepolymerised alone, or in admixture with each other or with alkenes toform random copolymers, or by charging the dienes to the reactionmixture sequentially, either with each other or with alkenes, to formblock copolymers.

R¹, R² and R³ are preferably independently selected from alkyl, aryl,and alkaryl. More preferably, each of the radicals R¹, R² and R³contains from 1 to 10 carbon atoms. In order to reduce the reactivity ofthe siloxy group on the initiator, the radicals R¹, R² and R³ arepreferably not all methyl and preferably together contain at least 4,most preferably at least 5, carbons atoms. In this way, a degree ofsteric hindrance is introduced into the silyl group which inhibitsreaction between that group and the living ends of the growing polymerchain, especially when at least one of R¹, R² and R³ contain at leastthree, more especially at least four, carbon atoms. Polymer yield andpurity is also generally enhanced if at least one of R¹, R² and R³ isaryl, preferably phenyl or mono-substituted phenyl with themono-substituent group on the phenyl preferably being a C₁ -C₅ alkylgroup.

The spacer group A is preferably contains at least two carbon atoms andis preferably a saturated hydrocarbon group such as a branched orstraight chain alkyl bridging group, though less preferably it maycontain at least one aromatic group such as a p-phenylene group. Theprincipal criteria for the selection of the group A is that it should besufficiently long to prevent the siloxy end group from interfering withthe polymerisation reaction, and it should provide the initiator withenhanced solubility in the inert, preferably non-polar solvent employedin the process. At the same time it should not add significantly to thesize and bulk of the terminal group at the end of the polymer chainbecause this will adversely affect the polymer's physical properties,especially its elastomeric properties. For these reasons, A is mostpreferably a straight chain alkyl bridging group of formula--(CH₂)--_(m) where m is an integer from 3 to 15, especially 3 to 10.

B is preferably lithium or sodium, and is most preferably lithium.

The present polymerisation reaction is preferably carried out at atemperature of between -31° C. and +30° C., especially between 10° C.and +10° C. The maximum temperature that may be employed in a givensystem will depend primarily on the physical properties, especially theboiling points, of the monomers and solvent chosen.

The amount of initiator added to the reaction mixture will be determinedby the structure of the monomer to be polymerised and by the desiredmolecular weight of the polymer. Typically for the production of apolymer containing a polymeric chain, derived from the polymerisation ofan olefinic-containing monomer and having a polymer molecular weightbetween about 1,000 and 100,000, between 0.5 and 50 mmoles of initiatoris used for each mole of monomer. The polymeric chain preferably has amolecular weight in the range 1,000 to 10,000 in which case preferablybetween 5 and 50 mmoles of initiator is used for each mole of monomer.

After propagation has been allowed to reach equilibrium, the singleactive ends on the living polymer chains may be terminated, by theaddition of suitable reagents which either donate a proton to orfunctionalise the anionic carbons. Proton donors such as water oralcohol yield terminally non-functional polymers. Preferably, however,the polymer chains will be terminated by a functional group. Examples ofsuitable end groups are:

a. hydroxyl, prepared by adding aldehydes, ketones or alkylene oxides,especially ethylene oxide;

b. carboxyl, prepared by adding CO₂ to the anionic polymer;

c. mercapto, prepared by adding sulphur, cyclic disulphides or cyclicsulphides such as ethylene or propylene sulphides;

d. amino and aziridine, prepared by adding aminoaldehydes orpolyaziridines such as phenyl-bis(2-methyl-1-aziridinyl) phosphineoxide;

e. epoxide, prepared by adding glycidaldehyde or diepoxides; and

f. metal halides, especially magnesium halides, prepared by adding ametal halide such as magnesium bromide.

Alternatively, the living polymer chains may be terminated by a di-orpolyfunctional coupling agent which is capable of terminating two ormore polymer chains through a single coupling agent molecule, therebylinking those chains together, with the advantage that a considerableincrease in polymer molecular weight can be achieved with littledegradation in polydispersivity. An example of such a coupling agent isSiCl₄, which by displacement of its chloro substituent groups yields a"star" polymer with four, organosiloxy-terminated polymer chainsradiation from a central silicon atom. Other polymers containing from 2or 3 to 20 polymer chain arms radiating from a central coupling agentmay be prepared utilising complex coupling agents such asmulti-functional organohalides typically containing from 2 or 3 to 20,preferably 2 to 4, halide groups, and other multi-functionalpolyhalosilanes preferably containing from 2 to 4 halide groups.Examples of such coupling agents are 1,2 ethylene dibromide, 1,4dichlorobutane, and dimethyldichlorosilane.

The organosiloxy protective groups remain unaffected by these varioustermination reactions. However, once propagation has been terminated,the relatively inert organosiloxy end groups on the polymer chains maythen be functionalised by reaction with a desilylation reagent to yield,after subsequent reaction with acid solution, reactive hydroxyl endgroups which are reactive in the sense that they can be reacted furtherto give rise to chemical cross-linking of the polymer chains. Preferredreagents for such desilylation reactions are the tetralkylammoniumfluorides, especially tetra-n-butylammonium fluoride, in polar solventssuch as alkyl or cycloalkyl ethers, especially tetrahydrofuran. Theseand other suitable desilylation reagents are discussed in Synthesis, 9,817-845 (1985), especially on page 828. Since aziridine and epoxidegroups may react with some of these reagents and/or acid solutions,these groups represent less preferred terminal groups on the other endsof the polymer chains prior to desilylation.

The present polymerisation process offers a number of significantadvantages over other known anionic polymerisation processes. First, themolecular weight distribution (M_(w) /M_(n)) is narrower than thatachieved by the analogous reaction using difunctional anionicinitiators. In the present case the molecular weight distribution (alsoknown as "polydispersivity") is typically about 1.1 whilst in thecompeting process M_(w) /M_(n) is for a polydiene generally 1.5 or abovein the absence of sterically-hindered Lewis acid and about 1.3 in thepresence of a sterically-hindered Lewis acid. The advantage offered by apolymer with a narrow M_(w) /M_(n) is that it produces a cured productwith a well defined network and, as a consequence, high strength.

The second advantage offered by the present process is the enhancementof the 1,4-content of the polydiene products it is capable of producingfrom the anionic polymerisation of 1,3-dienes. In the present process,polydienes with a 1,4-content of 90% can be routinely prepared, whereaswith difunctional initiators, the maximum 1,4-contents achievable isabout 50%. This advantage stems principally from the advantageoussolubility of the present initiator compounds in inert, non-polarhydrocarbon solvents which obviates the need to conduct polymerisationwithin a polar solvent.

A third advantage of the present invention is that it allows for thepreparation of polymers with a far greater diversity of functionalitythan has hitherto been achievable by anionic polymerisation.Monofunctional polymers result from termination with a proton donorfollowed by reactive functionalisation of the organosiloxy end groups(for example, to produce reactive hydroxyl end groups). Bifunctional(telechelic) polymers result from (a) functional termination of thepolymerisation reaction followed by (b) reactive functionalisation ofthe organosiloxy end groups. Indeed this can lead to telechelic polymershaving the same or different functional end groups depending on thereagents used in each of the steps (a) and (b), adding further to theaforesaid advantage of diversity. Di- and poly-functional polymersresult from termination of the polymerisation reaction with di- andpoly-functional coupling agents, followed by reactive functionalisationof the organosiloxy end groups.

The monofunctional silyl ether initiators which are used in the presentprocess are preferably prepared by the method of reacting, in an inertsolvent, the alkali metal B with an organosiloxyhalide of formula II##STR2## wherein R¹, R², R³ and A are as defined above and Z¹ representsa halogen. The reaction may be represented by the equation

    R.sup.1 R.sup.2 R.sup.3 Si--O--A--Z.sup.1 +2B→R.sup.1 R.sup.2 R.sup.3 Si--O--A--B+BZ.sup.1.

Z¹ is preferably chlorine or bromine, and is most preferably chlorine.

The reaction, which is exothermic, is preferably performed in anon-polar solvent. Preferred solvents are aliphatic, alicyclic andaromatic hydrocarbons, especially alkanes, cycloalkanes andcycloalkenes, having from 3-12, preferably from 4-8, carbon atoms. Mostpreferably, the solvent is the same as that used in the subsequentpolymerisation reaction.

The alkali metal B, which is preferably lithium, is preferably providedin particulate form such as chopped fine wire (typically 1-2 mmdiameter) or freshly cut chips. The particles are preferably subjectedto high speed agitation in a fluid suspension prior to use to produce aclean metallic surface for further reaction. If lithium is used, then itpreferably contains from 0.5-3%, more preferably 1-2%, by weight ofsodium. In the absence of sodium, lithium tends to be unreactive towardsorganic halides. However, with increasing sodium content, there is anincreasing likelihood of undesirable side reactions and above 5 wt %sodium, the reagents may react violently. It has been found that inorder to ensure a high yield of product initiator, a stoichiometricexcess of alkali metal must be used, of preferably at least 11/2-fold,more preferably at least two-fold, most preferably at least 21/2-fold,with an upper limit of preferably six-fold.

The reaction is preferably performed at a temperature of from 10° C. to50° C., more preferably from 20° C. to 40° C. At temperatures aboveabout 40° C., the production of undesirable organic by-products isobserved. The temperature can be controlled by cooling the reaction, andby ensuring that the major part of the organosiloxyhalide co-reagent isadded slowly to the alkali metal already in situ within the solvent. Areaction temperature of at least 30° C. is most preferred especially ifthe solvent is non-polar, to ensure that the reaction goes substantiallyto completion.

A further preferred condition of the reaction is that it should beperformed under a dry, oxygen-free inert gas. The gas is preferably anoble gas such as helium or argon, since nitrogen will react with thealkali metal to form a metal nitride, especially if the metal islithium.

The advantage of this method of initiator preparation is that theprincipal by-products of the reaction (alkali metal halide and excessalkali metal) are insoluble inorganic solids rather than reactive,solvent-soluble organic compounds and so are easily separated from thesoluble initiator compound before it is used in the subsequentpolymerisation process.

The organosiloxyhalide compound of general formula II may be prepared byreacting, in an inert solvent an alcohol of general formula III

    HO--A--Z.sup.1                                             III

with a silylhalide of general formula IV ##STR3## wherein Z² is ahalogen which is the same or different to Z¹ and is preferably chlorine.

The terminated polymers resulting from the present process represent anovel group of polymers which may be used as intermediates in thepreparation of further, functionally terminated polymers, especiallytelechelic polymers, by the subsequent conversion of the protectiveorganosiloxy end groups into hydroxyl functional groups.

According to a second aspect of the present invention, therefore, thereis provided a siloxy-terminated hydrocarbon polymer containing at leastone polymer chain per molecule of general formula V ##STR4## wherein R¹,R², R³ and A are as defined above, and --(M)_(n) -- represents apolymerised olefinic-containing monomer, preferably a polymerised alkeneor, more preferably, a polymerised 1,3-diene.

The polymer may be of general formula VI ##STR5## wherein X is selectedfrom H, carboxyl, hydroxyl, mercapto, amino and a metal halide,especially a magnesium halide, group. Such polymers are produced byterminating the living polymer chain produced by the present process bythe monofunctional reagents described above. Alternatively, the polymermay be of general formula VII ##STR6## wherein Y is the residue of a di-or multi-functional halide coupling agent containing q functional halidegroups, where q is an integer from 2 to 20 (for example, 3), especiallyfrom 2 to 4, and r is an integer of at least 2 (for example, 3) which isless or equal to q. For example, four-chain polymers of general formulaVII linked together by a single silicon atom can be produced by livingchain termination with the polyfunctional coupling agent SiCl₄.Similarly, polyfunctional organohalide coupling agents such as 1, 2ethylene dibromide and 1,4 dichlorobutane, and other polyfunctionalpolyhalosilane coupling agents such as dimethyldichlorosilane, may alsobe used.

Preferably, the polymeric chain --(M)_(n) -- has an average molecularweight in the range of 1,000 to 10,000, especially 2,000 to 7,000 inwhich case the polymers produced by the present invention will, if thepolymer molecules contain a single polymeric chain --(M)_(n) --,normally be liquids. If desired however semi-solid and solid polymerswith polymeric chains --(M)_(n) -- having an average molecular weight ofup to 100,000 or above may also be prepared.

The present invention will now be described by way of Example only.

MATERIALS

Butadiene (Matheson) was dried by passage through molecular sieves,calcium chloride and calcium hydride, before collecting in a graduatedvessel at -78° C.

Diethylether (BDH) was dried overnight over freshly cut sodium metal (2mm diameter wire), filtered and used immediately.

Diphenylacetic acid (BDH) was stored at 40° C. under vacuum for at least24 hours before use.

Hexane (BDH) was dried over calcium hydride and fractionally distilledunder nitrogen, the fraction boiling at 67°-8° C. being collected.Lithium metal (Fluke) containing 1-2% sodium was supplied as a 30% w/wdispersion in mineral oil. The metal was washed repeatedly with hexanebefore charging with the reaction solvent so as to prepare a cleansilvery white metal surface.

Tert-butyldimethylsiloxy 1-chloro-hexyl ether was fractionallydistilled, under reduced pressure prior to use, the fraction boiling at184°-5° C. (100 mmHg) being collected.

Tert-butyldiphenylsiloxy 1-chloro-hexyl ether was distilled from akugelrohr (oven temperature 215° C.) under reduced pressure (1 mmHg),just prior to use.

Terta-butyldiphenylsiloxy 1-chloro-propyl ether was distilled from akugelrohr (oven temperature 200° C.) under reduced pressure (1 mmHg),just prior to use.

Tetra-n-butylammonium fluoride (Aldrich) was supplied as a 1.0M solutionin tetrahydrofuran and used directly.

Tetrahydrofuran (BDH), stabilised with 0.1% quinol, was distilled undernitrogen when required after sufficient sodium benzophenone solution inTHF had been added to yield a permanent purple colour.

GENERAL PROCEDURE

All experimental techniques were performed under an inert atmosphere, beit oxygen-free nitrogen or argon. All glassware, except syringes, wascleaned by successive washing with 10% hydrofluoric acid, distilledwater and acetone. It was then dried and stored in an oven at 120° C.until required. All additions, excepting that of alkali metals, wereperformed via syringe.

EXAMPLE 1

A sixfold excess of lithium slurry (10 g) in mineral oil was placed intoa 500 ml 3-necked round bottom flask equipped with serum cap, argoninlet/outlet, water condenser, thermometer and magnetic follower. Theslurry was then repeatedly washed with hexane, by high speed agitation,until a clean silvery white metal surface was obtained. The lithiummetal was then charged with further hexane (100 ml) which was to act asthe reaction solvent. The temperature inside the reaction flask was thenraised to 35° C. and allowed to reach thermal equilibrium over the spaceof thirty minutes.

Freshly distilled tert-butyldimethyl (tBDM-) siloxy-1-chlorohexyl ether(5 g, 0.02 mol) was injected into the reaction vessel. A primaryexotherm wasobserved to commence after 5-10 minutes. This exotherm wascontrolled by the utilisation of cold air cooling which maintained theflask temperaturebelow 45° C. throughout the course of the reaction.Four further aliquots of tBDM-siloxy-1-chlorohexyl ether (4×5 g, 0.08mol) were added over a period of 1-2 hours. The reaction was allowed toproceed for a further 2 hours before allowing the products to settleinside the flask.The crude supernatant hexane solution oftBDM-siloxy-1-lithiohexyl ether could then be extracted via syringe andutilised in various reactions, or simply quenched with methanol toproduce tBDM-siloxy hexane (Yield 95%). The yield of the reaction wasconfirmed by ¹ H n.m.r. spectroscopy and i.r. spectroscopy.

EXAMPLE 2

The procedure of Example 1 was repeated except that the species to belithiated was tert-butyldiphenyl (t-BDP-) siloxy-1-chlorohexyl etherrather than tert-butyldimethylsiloxy-1-chlorohexyl ether. The resultantyield of the reaction was again greater than 90%.

EXAMPLE 3

The procedure of Example 1 was repeated except that the reaction wasexecuted within the temperature range 20°-30° C., and the reactionsolvent was diethylether instead of n-hexane. The resultant yieldof thereaction was again greater than 90%.

EXAMPLE 4

The procedure of Example 1 was repeated except that the species to belithiated was tert-butyldiphenylsiloxy-1-chloropropyl ether rather thantert-butyldimethylsiloxy-1-chlorohexyl ether. The reaction was executedwithin the temperature range 20°-30° C., and the reaction solvent wasdiethylether instead of n-hexane. The resultant yield of the reactionwas again greater than 90%.

EXAMPLE 5

The procedure of Example 1 was repeated except that the species to belithiated was tert-butyldiphenylsiloxy-1-chloropropyl ether rather thantert-butyldimethylsiloxy-1-chlorohexyl ether. The reaction was executedwithin the temperature range 20°-30° C. The resultant yield of thereaction was only 25% after 17 hours.

                  TABLE 1                                                         ______________________________________                                        The Effect of Temperature and Solvent Upon the Preparative                    Yield of Trialkyl/aryl Siloxy Lithioalkyl Ethers                              Trialkyl/Arylsiloxy                                                           Lithioalkyl Ether                                                                              Solvent  Temperature                                                                              Yield                                    ______________________________________                                        tBDM-siloxy lithiohexyl ether                                                                  Hexane   35-40° C.                                                                         >90%                                       "              Ether    20-30° C.                                                                         >90%                                     tBDP-siloxy      Hexane   35-40° C.                                                                         >90%                                     tBDP-siloxy lithiopropyl ether                                                                 Ether    20-30° C.                                                                         >90%                                       "              Hexane   20-30° C.                                                                          25%                                     ______________________________________                                    

EXAMPLE 6

Hexane (250 ml) was placed in a 500 ml round bottom 3-necked flaskequippedwith magnetic follower, thermometer, serum cap and nitrogeninlet/outlet. The reaction vessel was then chilled to -78° C. andbutadiene (30 ml) distilled into the system. The reaction mixture wasthen gradually allowed to warm to -5° C. and tBDM-siloxy 1-lithiohexylether (0.011 mol) in hexane solution from Example 1 was introduced byinjection in order to initiate polymerisation. Propagation was allowedto proceed atthis temperature for an hour, before the ice bath wasremoved and the reaction mixture gradually allowed to reach roomtemperature. Propagation was then allowed to continue at roomtemperature for a further 16 hours. Termination of the living ends wasthen accomplished typically by the injection of a five-fold excess ofmethanol (1 ml) to yield a water white polymer solution. This wassubsequently reduced in volume by rotary evaporation, precipitated intoexcess methanol (1000 ml) and the crude polymer syrup collect ondecanting. The work up produced a monofunctional polybutadiene with asiloxyl group on one end of the polymer chain. The product was found tobe of low molecular weight (2,100., to be relatively monodisperse (M_(n)/M_(w) =1.1) and to possess a high 1.4 percentage content (89%).

The molecular weight of the product was determined by gel permeationchromatography (gpc) in which measurements were carried out using aWaters840 chromatograph fitted with refractive index and ultra-violetdetectors in series. Four styragel columns (Polymer Laboratories) ofporosity 10⁵ Å, 10⁴ Å, 10³ Å and 10² Å were used, and the molecularweight was determined from a universal polystyrenecalibration curveusing the Mark-Houwinck co-efficients a=0.693, K=4.03×10⁻⁴ (high 1,2)and K=4.57×10⁻⁴ (high 1,4).

The percentage 1,4 content of the product was determined by ¹ H nuclearmagnetic resonance (nmr) spectroscopy in which measurements were carriedout on a Varian Associates EM 60 MHz spectrometer, samples of thepolymer being prepared as 10% w/v solutions in deuterochloroform.

EXAMPLE 7

The procedure of Example 6 was repeated except the reaction wasinitiated with tBDP-siloxy lithiohexyl ether from Example 2 rather thanwith tBDM-siloxy lithiohexyl ether.

EXAMPLE 8

The procedure of Example 6 was repeated except that the reaction wasterminated with excess ethylene oxide rather than excess methanol. Theusual work up procedure produced a bifunctional polybutadiene, with ahydroxyl group at one end of the chain and a siloxyl group at the other.

EXAMPLE 9

The procedure of Example 6 was repeated except that the reaction wasterminated with exactly 0.0055 mol of dichlorodimethylsilane rather thanexcess methanol. The usual workup procedure produced a difunctionalpolybutadiene (M_(n) /M_(w) between 1.1 and 1.2 and % 1,4 contentbetween 87% and 91%) possessing siloxyl groups at both ends and acentral dimethylsilyl chain-linking group.

EXAMPLE 10

Siloxyl terminated polybutadiene (1 g) from Example 6 was dissolved intetrahydrofuran (20 ml) in a 100 ml round bottom 3-necked flask equippedwith magnetic follower, serum cap and nitrogen inlet/outlet.Tetra-n-butylammonium fluoride (1.0M) in tetrahydrofuran (1.1 ml) wasthenadded by injection and the reaction allowed to proceed at 20° C.for2 hours. Afterwards the solution was added dropwise to excessmethanol, allowed to settle and the liquors decanted off to yield a paleyellow syrup, which was identified as monofunctional hydroxyl terminatedpolybutadiene (M_(n) /M_(w) =1.15, and % 1,4 content=90%).

EXAMPLE 11

The procedure of Example 10 was repeated using as the starting polymerthe siloxy-terminated polybutadiene products of Example 7 rather thanthe product of Example 6, to yield a monofunctional hydroxy-terminatedpolybutadiene (M_(n) /M_(w) between 1.1 and 1.2, and % 1,4 contentbetween 87% and 91%).

EXAMPLES 12 AND 13

The procedure of Example 10 was repeated using as the starting polymerthe siloxy-terminated polybutadiene products of Examples 8 and 9 in turnrather than the product of Example 6. In both cases, the siloxy groupson the starting polymers were replaced by hydroxy groups, to yielddifunctional hydroxy-terminated polybutadienes (M_(n) /M_(w) between 1.1and 1.2, % 1,4 content between 87% and 91%).

We claim:
 1. Process for the anionic polymerisation of anolefinic-containing monomer comprising contacting the monomer in aninert solvent with a monofunctional silyl ether initiator of the formulaI ##STR7## wherein R¹, R² and R³ are independently selected fromsaturated and unsaturated aliphatic and aromatic radicals, A is ahydrocarbon bridging group containing from 1 to 25 carbon atoms, and Bis an alkali metal.
 2. Process according to claim 1 wherein the monomercomprises a 1,3-diene.
 3. Process according to claim 1 wherein each ofR¹, R² and R³ contains from 1 to 10 carbon atoms and R¹, R² and R³together contain at least 5 carbon atoms.
 4. Process according to claim1 wherein --A-- is --(CH₂)_(m) -- where m is an integer from 3 to
 15. 5.Process according to claim 1 wherein, after propagation has ceased, theliving polymer chains are terminated by a proton or a functional group,or are linked together by a di- or poly-functional linking agent. 6.Process according to claim 5 wherein the functional group is selectedfrom carboxyl, hydroxyl, mercapto, amino, and a metal halide.
 7. Processaccording to claim 5 wherein the linking agent comprises a halosilane oran organohalide.
 8. Process according to claim 5 wherein, after theliving polymer chains are terminated or linked together, theorganosiloxy terminal groups on the polymer chains are desilylated andprotonated to convert said groups into functional hydroxyl groups.
 9. Asiloxy-terminated hydrocarbon polymer containing at least one polymerchain per molecule of the formula: ##STR8## wherein R¹, R², R³ areindependently selected from saturated and unsaturated aliphatic andaromatic radicals, A is a saturated hydrocarbon bridging groupoptionally containing at least one aromatic group, --(M)_(n) --represents a polymer of an olefinic containing monomer, n has a valuesuch that the average molecular weight of the polymeric chain is fromabout 1,000 to about 100,000, and X is selected from carboxyl, hydroxy,mercapto, amino, and a metal halide group.